Detergent forming monocarboxy acid esters of certain oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 DETERGENT FORMING MONOCARBOXY ACID ESTERS OFCERTAIN OXYALKYL- ATED PHEINOL-ALDEHYDE RESINS' Melvin De Groote, St.Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to PetroliteCorporation, Ltd., Wilmington, Del., a corporation of Delaware NoDrawing. Application December 1-0, 1948, Serial No. 64,455

7 Claims. (01. 260-19) The present invention is concerned with certainnew chemical products, compounds or compositions, having usefulapplications in various arts. This invention is a continuation-in-partof our co-pending application, Serial No. 726,212, filed February 3,1947, now abandoned. It include methods or procedures for manufacturingsaid new products, compounds or compositions, as well as the products,compounds or compositions themselves. Said new compositions are estersin which the acyl radical is that of a detergent-forming monocarboxyacid having at least 8 and not over 32 carbon atoms, and the alcoholicradical is that of certain hydrophile polyhydric synthetic products;said hydrophile synthetic products being oxyalkylation products of (A)an alpha-beta 'alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, butylene oxide,propylene oxide, glycide and methylglycide, and (B) anoxyaikylation-susceptible, fusible, organic solvent-soluble,water-insoluble phenol-aldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said'resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is a hydrocarbon radical havingat least 4 and not more than 12 carbon atoms and ubstituted in the 2,4,6position; said oxyalkylated resin being characterized by theintroduction into the resin molecule of a plurality of divalent radicalshaving the formula (R)n, in which R1 is a member selected from the classconsisting of ethylene radicals, propylene radicals, butylene radicals,hydroxypropylene radicals, and hydroxybutylene radicals, and n is anumeral varying from 1 to 20; with the proviso that at least 2 moles ofalkylene oxide be introduced for each phenolic nucleus. 1

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil type that are commonly referred to as cutoil, roily oil, emulsified oil, etc.', and which comprise fine dropletsof naturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion. This specific application is described andclaimed in our co-pending application, Serial No. 64,454, filed December10, 1948, now Patent No. 2,541,995 issued February 20, 1951. See alsoour co-pending application, Serial No. 64,469, filed December 10, 1948.

The new products are useful as wetting, detergent and levelling agentsin the laundry, textile and dyeing industries; as wetting agents anddetergent in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in roadbuilding andthe like; as a flotation reagent in the flotation separation of variousaqueous suspensions containing negatively charged particles such assewage, coal washing waste water, and various trade wastes and the like;as germicides, insecticides, emulsifying agents, as for example, forcosmetics, spray oils, water-repellent textile finishes as lubricants,etc.

For purpose of convenience what is said hereinafter will be divided intothree parts. Part 1 will be concerned with the production of the resinfrom a difunctional phenol and an aldehyde; Part 2 will be concernedwith the oxyalkylation of the resin so as to convert it into ahydrophile hydroxylated derivative; and Part 3 will be concerned withthe conversion of the immediately aforementioned derivative into a totalor partial ester by reaction with an acid, an ester, or other functionalderivative, so as to obtain a compound of the kind previously specifiedand subsequently described in detail.

PART 1 I OH OH H H C H In such idealized representation 11. is a.numeral varying from 1 to 1'3 01' even more, provided that the resin isfusible and organic solvent-soluble. R. is a hydrocarbon radical havingat least 4 and not over 8 carbon atoms. In the instant application R mayhave as many as 12 carbon atoms, as in the case of a resin obtained froma dodeoylphenol. In the instant invention it may be first suitable todescribe the alkylene oxides employed as reactants, then the aldehydes,and finally the phenols, for the reason that the latter require a moreelaborate description.

The alkylene oxides which may be used are the alpha-beta oxides havingnot more than 4 carbon atoms, to wit, the alpha-beta ethylene oxide,alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, andmethylgly'cide.

Any aldehyde capable of f "rming a methylol or a substituted methylolgroup and having not more than 8 carbon atoms is satisfactory. so long.as it does not possess some other functional group or structure whichwill conflict with the resinification reaction or with the subsequentoxyalkylation of the resin, but the use of formaldehyde,

in its cheapest form of an aqueous solution, for

the production of the resins is particularly advantageous. Solidpolymers of formaldehyde are more expensive and higher aldehydes areboth less reactive, and are more expensive. Furthermore, the higheraldehydes may undergo other 1;

reactions which are not desirable, thus introducing difiicultiesinto theresinification step. Thus acetaldehyde, for example, may undergo analdol condensation, and it and most of the higher aldehydes enter intoself-resinification when treated with strong acids or alkalies. On theother hand, higher aldehydes frequently beneficially affect thesolubility and fusibility of a resin. This is illustrated, for example,by the different characteristios of the resin prepared from paratertiaryamylphenol and formaldehyde on one hand, and a comparable productprepared from the same phenolic reactant and heptaldehyde on the otherhand. The former, as shown in certain subsequent examples, is a hard,brittle, solid, whereas the latter is soft and tacky, and obviouslyeasier to handle on the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly ben'zal'dehyde. Theemployment of fu'rfu'ral requires careful control for the reason that inaddition to its aldehydic function, furfural can form condensations byvirtue of its unsaturated structure. The production of resins fromforfural for use in preparing products from the present process is mostconveniently conducted with weak alkaline catalysts and often withalkali metal carbonates. Useful 'aldehydes, in addition to formaldehyde,are acetaldehyde, propioni'c aldehyde, butyraldehyde, Z-ethylhexanal,ethylbutyraldehyde, heptaldehyde, and ben'zaldehyde, furfural andglyoxal. It would appear that the use of glyoxal should be avoided dueto the fact that it is tetrafunctional. rience has been that, in resinmanufacture and particularly as described herein, apparently only one ofthe aldehydic functions enters into the resinification reaction. Theinability of the However, our expeother aldehydic function to enter intothe reaction is presumably due to steric hindrance. Needless to say, onecan use a mixture of two or more aldehydes although usually this has noadvantage.

Resins of the kind which are used as intermediates in this inventionareobtained with the use of acid catalysts or alkaline catalysts, orwithout the use of any catalyst at all. Among the useful alkalinecatalysts are ammonia, amines, and quaternary ammonium bases. It isgenerally accepted that when ammonia and amines are employed ascatalysts they enter into the condensation reaction and, in fact, mayoperate by initial combination with the aldehydic reactant. The compound'hexa'methylehetetramin'e illustrates such a combination. In light ofthese various reactions it becomes difiicult to present any formulawhich would depict the structure of the various resins priortooxyalkylation. More will be said subsequently as to the differencebetween the use of an alkaline catalyst and an acid catalyst; even inthe use of an alkaline catalyst there is considerable evidence toindicate that the products are not identical where different basicmaterials are employed. The basic materials employed include not onlythose previously enumerated but also the hydroxides of the alkalimetals, hydroxides of the alkaline earth metals, salts of strong basesand weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Paratertiarybutylphenol; part-secondary butylphenol; paratertiar-y-ainylphenol; parasecondary=-amy1phenol;para-teTtiariYhexylphenol; para isooctylphenol; ortho phenylphenol;para-phenylphenol; ortho benzylphenol; para-benzylphenol; and paracyclohexylphenol, and the corresponding .ortho para substitutedmetacresols and 3,5-xylen'ols. Similarly, one may use paraorortho-n'onylphenol or a mixture, paraor decylphenol or a mixture,menthylphenol, or paraor orth'o dodecylphenol.

The phenols herein contemplated for reaction may be indicated by thefollowing formula:

on R" R in which R is selected from the class consisting of hydrogenatoms and hydrocarbon radicals having at least 4 carbon atoms and notmore than 12 carbon atoms, with the proviso that one occurrence of R isthe hydrocarbon substituent and the other two occurrences are hydrogenatoms, and with the further provision that one or both of the 3 and 5positions may be methyl substituted.

The above formula possibly can be restated more conveniently in thefollowing manner, to wit, that the phenol employed is of the following;formula, with the proviso that R is ahydr'ocarbon substituent located inthe 2,4,6 position, again with the provision as to 3 or 3,5 methylsubstitution. This is conventional nomenclature, numbering the variouspositions in the usual clockwise manner, beginning with the hydroxylposition as one:

The manufacture of thermoplastic phenolaldeh yde resins, particularlyfrom formaldehyde and a difunctional phenol, i. e., a phenol in whichone of the three reactive positions (2,4,6) has been substituted by ahydrocarbon group, and particularly by one having at least 4 carbonatoms and not more than 12 carbon atoms, is well known. As has beenpreviously pointed out, there is no objection to a methyl radicalprovided it is present in the 3 or 5 position.

These resins, used as intermediates to produce the products of thepresent invention are described in detail in our Patent 2,499,370,granted March '7, 1950, and specific examples of suitable resins arethose of Examples la through 103a of that patent, and reference is madethereto for a description of these intermediate resins and for examplesthereof.

PART 2 Having obtained a suitable resin of the kind described, suchresin is subjected to treatment with a low molal reactive alpha-betaolefin oxide so as to render the product distinctly hydrophile in natureas indicated by the fact that it becomes self-emulsifiable or miscibleor soluble in water, or self -dispersible, or has emulsifyingproperties. The olefin oxides employed are characterized by the factthat they contain not over -l carbon atoms and are selected from theclass consisting of ethylene oxide, propylene oxide. butylene oxide,glycide, and methylglycide. Glycide may be, of course, considered as ahydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide.In any event, however, all such reactants contain the reactive ethyleneoxide ring. and may be best considered as derivatives of or substitutedethylene oxides. The solubilizing efiect of the oxide is directly pro-,portional to the percentage of oxygen present, or specifically, to theoxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is2:3; and in methyl glycide, 1 22. In such compounds, the ratio isveryfavorable to the production of hydrophile or surface-activeproperties. However, the ratio, in propylene oxide, is 1:3, and inbutylene oxide, 1:4. Obviously, such latter two reactants aresatisfactorily employed only where the resin composition is such as tomake incorporation of the desired property practical. In other cases,they may produce marginally satisfactory derivatives, or evenunsatisfactory derivatives. They are usable in conjunction with thethree more favorable alkylene oxides in all cases. For instance, afterone or several propylene oxide or butylene oxide molecules have beenattached to the resin molecule, oxyalkylation may be satisfactorilycontinued using the more favorable members of the class, to produce thedesired hydrophile product. Used alone, these two reagents may in somecases fail to produce sufficiently hydrophile derivatives because oftheir relatively low oxyen-carbon ratios.

Thus, ethylene oxide is much more efiective than propylene oxide, andpropylene oxide is more effective than butylene oxide. propylene oxide(glycidel is more effective than propylene oxide. Similarly, hydroxybutylene oxide (methyl glycide) is more effective than butylene oxide.Since ethylene oxide is the Hydroxy cheapest alkylene oxide availableand is reactive,

its use is definitely advantageous, and especially in light of its highoxygen content. Propylene oxide is less-reactive than ethylene oxide,and butylene oxide is definitely less reactive than propylene oxide. Onthe other hand, glycide may react with almost explosive violence andmust be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactantsused in the practice of the present invention are prepared isadvantageously catalyzed by the presence of an alkali. Useful alkalinecatalysts include soaps, sodium acetate, sodium hydroxide, sodiummethylate, caustic potash, etc. The amount of alkaline catalyst usuallyis between 0.2% to 2%,. The temperature employed may vary from roomtemperature to as high as 200 C. The reaction may be conducted with orwithout pressure, i. e., from zero pressure to approximately 200 or even300 pounds gauge pressure (pounds per square inch). In a general way,the method employed is substantially the same procedure as used foroxyalkylation of other organic materials having reactive phenolicgroups.

It may be necessary to alolw for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. Forinstance, ifa nonvolatile strong acid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal stoichiometrically. to such acidity, andinclude added alkali over and above this amount as the alkalinecatalyst.

It is advantageous to conduct the oxyethylation in presence of an inertsolvent such as xylene, cymene, decalin, ethylene glycol diethylether,diethyleneglycol diethylether, or the like, although with many resins,the oxyalkylation proceeds satisfactorily without a solvent. Sincexylene is cheap and may be permitted to be present in the final productused as a demulsifier, it is our preference to use xylene. This isparticularly true in the manufacture of products from low-stage resins,i. e., of 3 and up to and including 7 units per molecule.

. .If a xylene solution is used in an autoclave as hereinafterindicated, the pressure readings of course represent total pressure,that is, the combined pressure due to xylene and also due to ethyleneoxide or whatever other oxyalkylating agent is used. Under suchcircumstances it may be necessary at times to use substantial pressuresto obtain eifective results, for instance, pressures up to 300 poundsalong with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of two ways: After theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point of the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or'some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Another suitable procedure is to use propylene oxide or butylene oxideas a solvent as well as a reactant in the earlier stages along withethylene oxida for instance, by dissolving the powdered resin inpropylene oxide even though oxyalky-lation is taking place to a greateror lesser degree. After a solution has been obtained which representsthe original resin dissolved in propylene oxide or butylene oxide, 'or amixture which includes the oiqralkylated product, ethylene oxide isadded to react with the liquid mass until hydrophile properties areobtained, Since ethylene oxide is more reactive than propylene oxide orbutylene oxide, the final product may contain some unreacted propylene,oxide or butylene oxide which can be eliminated by volatillzation ordistillation in any suitable manner.

Attention is directed to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible resins invariablyare soluble in one or more organic solvents such as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed, solventswhich are susceptible to oxyalky-lation are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. ever, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the organic solvent-soluble resin can be finely powdered, forinstance to 190 to 200 mesh, and a slurry or suspension prepared inxylene or the like, and subjected to oxyalkylation. The fact that theresin is soluble in an organic solvent or the fact that it is fusiblemeans that it consists of separate molecules. Phenol aldehyd'c resins ofthe typeherein specified possess reactive hydroxyl groups and areoxyalkylation susceptible.

Considerable of what is said immediately here-'- inafter is concernedwith ability to vary the hydrophile properties of the hydroxylatedintermediate reactants from minimum hydrophile properties to maximumhydrophile properties. Such properties in turn, of course, are efiectedsubsequently by the acid employed for esterification and thequantitative nature of the esterfi cationitselr", i. e., whether it istotal or partial. It may be well, however, to point out what has beensaid elsewhere in regard to the hydroxylated intermediate reactants.See, for example, our co-pending applications, Serial Nos. 8,730 and8,731, both filed February 16, 1948, and Serial No. 42,133, filed August2, 1948,, and Serial No.

42,134, filed August 2, 1948, all now abandoned.

lhe reason is that the esterification, depending on the acid selected,may vary the hydrophilehydrophobe balance in one direction or the other,and also invariably causesthe development of some property which makesit inherently different from the two reactants from which the derivativeester is obtained.

Referring to the hydroph'ile 'hydroxylated intermediates, even moreremarkable and equally difficult t ex lain, are the versatility and theutilityof these compounds considered as chemical reactants as one goesfrom minimum hydrophile property to ultimate maximum hydrophileproperty. For instance, minimum hydrophile property may be describedroughly as the point where two ethyleneoxy radicals or moderately inexcess thereof are introduced per phenolic hydroxyl. Such minimumhydrophile property or sub-'surfa-ce-activity 'or minimum suriaceactivity means that the product shows at Howleast emulsifying propertiesor self-dispersion in cold or even in warm distilled water (15 to 40 C.)in concentrations of 0.5% to 5.0%. These materials are generally moresoluble in cold water than warm water, and may even be very insoluble inboiling water. Moderately high temperatures aid in reducing theviscosity of the solute under examination. Sometimes if one continues toshake a hot solution, even though cloudy or containing an insolublephase, one finds that solution takes place to give a homogeneous phaseas the mixture cools. Such selfdispersion tests are conducted in theabsence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum(.2 moles of ethylene oxide per phenolic nucleus or the equivalent) butinsuflicient to give a sol as described immediately preceding, then, andin that event hydrophile properties are indicated by the .fact that onecan produce an emulsion by having present 10% to 50% of an inert solventsuch as xylene. All that one need to do to have a xylene solution Withinthe range of 50 to parts by weight of oxyalkylated derivatives and 50 to10 parts by weight of xylene and mix such solution with one, two orthree times its volume of distilled water and shake vigorously so as toobtain an emulsion which may .be of the oil-in-water type or thewater-in-oil type (usually the former.) but, in any event, is due to thehydrophile-hydrophobc balance of the oxyalkylated derivative. We prefersimply to use the xylene diluted derivatives, which are describedelsewhere, for this test rather than evaporate the solvent and employanymore elaborate tests, if the solubility is not sufficient to permitthe simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethylor methyl alcohol, ethylene glycol diethylether, or diethylene glycoldiethylether, with a little acetone added if required, making a ratherconcentrated solution, for instance 40% to 59%, and then'adding enoughof the concentrated alcoholic or equivalent solution to give thepreviously suggested 0.5% to 5.9% strength solution. If the product isselfdispersing (i. e., if the oxyalkylated product is a liquid or aliquid solution self-emulsifiable),

such sol or dispersion is referred to as at least semi-stable in thesense that sols, emulsions, or dispersions prepared are relativelystable, if they remain at least for some period of time, for instance 30minutes to two hours, before showing any marked separation; Such testsare conducted at room temperature (22 'C.). Needless to say, a test canbe made in presence of an insoluble solvent such as 5% to 15% of xylene,as noted in previous examples. 'If such mixture, 1. e., containing awater-insoluble solvent, is at least semi-stable, obviously thesolvent-free product would be even more so. Surface-activityrepresenting an advanced hydrophile-hydrophobe balance can also bedetermined by the use of conventional measurements hereinafterdescribed. One outstanding characteristic property indicatingsurface-activity in a material is the ability to form a permanent foamin dilute aqueous solution, for example, less than 0.5%, when in thehigher oxyal'kylated stage, and to form an emulsion in the lower andintermediate stages 'of oxyalkylatio'n.

Allowance must be made for the presence of a solvent inthe fmal productin relation to the hydrophile properties of the :final product. Theprinciple involved in the manufacture of "the herein contemplatedcompounds for useas polyhydric reactants is based on the conversion of ahydrophobe or non-hydrophile compound or mixture of compounds intoproducts which-are distinctly hydrophile, at least to the extent thatthey have emulsifying properties or are selfemulsifying; that is, whenshaken with water they produce stable or semi-stable suspensions, or, inthe presence of a water-insoluble solvent, such as xylene, an emulsion.In' demulsification, it is sometimes preferable to use a product havingmarkedly enhanced hydrophile properties over and above the initial stageof self-emulsifiability, although we have found that with products ofthe type used herein, most efficacious results are obtained withproducts which do not have hydrophile properties beyond the stage ofself-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols whichshow typical properties comparable to ordinary surface-active agents.Such conventional surface-activity may be meas ured by determining thesurface tension and the interfacial tension against parafiin oilor thelike. At the initial and lower stages of oxyalkylation, surface-activityis not suitably determined in this same manner but one may employ anemulsification test. Emulsions come into existence as a rule through thepresence of a surface-active emulsifying agent. Some surface-activeemulsifying agents such as mahogany soap may produce a water-in-oilemulsion or an oil-in-water emulsion depending upon the ratio of the twophases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylaticn, the so-calledsubsurfaceactive stage. The surface-active properties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis. as follows: The oxyalkylated resin is dissolved in an equal weightof xylene. Such 50-50 solution is then mixed with 1-3 volumes of waterand shaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-inwater type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At' times,particularly in the lowest stage of oxyalkylation, one may obtain awater-in-xylene emulsion which is apt to reverse on more and furtherdilution with water.

If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst'and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4 units per resin molecule. Such resin, when diluted with an equalweight of xylene, will serveto illustrate the above emulsification test.

In a few instances, the resin may not be sumciently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. such mixture. or any other similarmixture, is

(water-in-oil type) vigorous shaking It is understood that 10 consideredthe equivalent of xylene for the purpose of this'test.

In many cases, there isno doubt as to the presence or absence ofhydrophile or surface-active characteristics in the polyhydric reactantsused in accordance with this invention. They dissolve or disperse inwater; and such dispersions foam readily. With borderline cases, i. e.,those which show only incipient hydrophile or surfaceactive property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. The fact that a reagent is capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile; In doubtful cases, comparison can be made with thebutylphenolformaldehyde resin analog wherein 2 moles of ethylene oxidehave been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it-is desirableto determine the approximate point where self-emulsification begins,then it is better to eliminate the xylene or equivalent from a smallportion of the reaction mixture and test such portion. In some cases,such xylenefree resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrop-hileproperties may be the capacity of the material to'emulsify an insolublesolvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientself-emulsification' or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added water-insoluble solvent and minor pro-'portions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it is really immaterialwhether a xylene solution produces a sol or whether it merely produces;

anemulsion.

In light of what has been said previously in regard to the variation ofrang of hydrophile properties, and also in light of what has'bee'n' saidas tothe variation in the effectiveness of various alkylene oxides, andmost particularly of all ethylene oxide, to introduce hydrophilecharacter, it becomes obvious that there is a wide variation in theamount of alkylene oxide employed, as long as it is at least 2 moles perphenolic nucleus, for producing products useful for the practice of thisinvention. Another variation is the molecular size of the resin chainresulting from reaction between the difunctional phenoland the aldehydesuch as formaldehyde. It is well known that the' size and nature orstructureof the resin polymer obtained varies somewhat with theconditions of reaction, the proportions of reactants, the nature of thecatalyst, etc.

Based on molecular Weight determinations, most of the resins prepared asherein described, particularly in the absence of a secondary heatingstep, contain 3 to 6 or 7 phenolic nuclei with approximately 4 /2 or 5nuclei as an average. More drastic conditions of resinification yieldresins of greater chain length. Such more intensive resinification is aconventional procedure and may be employed if desired. Molecular weight,of course, is measured by any suitable procedure, particularly bycryoscopic methods; but using the same reactants and using more drasticconditions of resinification one usually finds that higher molecularweights are indicated by higher melting points of the resins and atendency to decreased solubility. See what has been said elsewhereherein in regard to a secondary step involving the heating of a resinwith or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalystis advantageously used in preparing the resin. A combination ofcatalysts is sometimes used in two stages; for instance, an alkalinecatalyst is sometimes employed in a first stage, followed byneutralization and addition of a small amount of acid catalyst in asecond stage. It is generally believed that even in the presence of analkaline catalyst, the number of moles of aldehyde, such asformaldehyde, must be greater than the moles of phenol employed in orderto introduce methylol groups in the intermediate stage. There is noindication that such groups appear in the final resin if prepared by theuse of an acid catalyst. It is possible that such groups may appear inthe finished resins prepared solely with an alkaline catalyst; but wehave never been able to confirm this fact in an examination of a largenumber of resins prepared by ourselves. Our preference, however, is touse an acid-catalyzed resin, particularly employing aformaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have beenable to determine, "such resins are free from methylol groups. As amater of fact, it is probable that in acid-catalyzed resinifications,the methylol structure may appear only momentarily at the very beginningof the reaction and in all probability is converted at once into a morecomplex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to preparepolyhydric reactants for use in the preparation of compounds employed inthe present invention, is to determine the hydroxyl value by theVerley-Biilsing method or its equivalent. The resin as such, or in theform of a solution as described, is then treated with ethylene oxide inpresence of 0.5% to 2% of sodium methylate as a catalyst in stepwisefashion. The conditions of reaction, as far as time or per cent areconcerned, are within the range previously indicated. With suitableagitation the ethylene oxide, it added in molecular proportion, combineswithin a comparatively short time, for instance a few minutes to 2 to 6hours, but in some instances requires as much as 8 to 24 hours. A usefultemperature range is from 125 to 225 C. The completion of the reactionof each addition of ethylene oxide in step wise fashion is usuallyindicated by the reduction or elimination of pressure. An amountconveniently used for each addition is generally equivalent to a mole ortwo moles of ethylene oxide per hydroxyl radical. When the amount ofylene oxide added is equivalent to approximately 50% by weight of theoriginal resin, a sample is tested for incipient hydrophile propertiesby simply shaking up in water as is, or after the elimination of thesolvent if a solvent is present. The amount of ethylene oxide used toobtain a useful demulsifying agent as a rule varies from 70% by weightof the original resin to as much as five or six times the weight of theoriginal resin. In the case of a resin derived from para-tertiarybutylphenol, as little as by weight of ethelyne oxide may give suitablesolubility. With propylene oxide, even a greater molecular proportion isrequired and sometimes a resultant of only limited hydrophile propertiesis obtainable. The same is true to even a greater extent with butyleneoxide. The hydroxylated alkylene oxides are more effective insolubilizing properties than the comparable compounds in which. nohydroxyl is present.

Attention is directed to the fact that in the subsequent examplesreference is made to the stepwise addition of the alkylene oxide, suchas ethylene oxide. It is understood, of course, there is .no objectionto the continuous addition of alkylene oxide until the desired stage ofreaction is reached. In fact, there may be less of a hazard involved andit is often advantageous to add the alkylene oxide slowly in acontinuous stream and in such amount as to avoid exceeding the higherpressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced fromdifunctional phenols and some of the higher aliphatic aldehydes, such asacetaldehyd'e, the resultant is a comparatively soft or pitch-like resinat ordinary temperatures. Such resins become comparatively fluid at toC. as a rule, and thus can be readily oxyalkylated, preferablyoxyethylated, without the use of a solvent.

What hasbeen said previously is not intended to suggest that anyexperimentation is necessary to determine the degree of oxyalkylation,and particularly oxyethylation. What has been said previously issubmitted primarily to emphasize the fact" that these remarkableoxyalkylated resins having surface activity show unsual properties asthe hydrophile character varies from a minimum to an ultimate maximum.One should not underestimate the utility of any of these polyhydricalcohols in a surface-active or sub-surface active range withoutexamining them by reaction with a number of the typical esters hereindescribed and subsequently examining the resultant for utility, eitherin demulsifioation or in some other art or industry as referred toelsewhere, or as a reactant for the manufacture of more complicatedderivatives. A few simple laboratory tests which can be conducted in aroutine manner will usually give all the information that is re quired.

For instance, a simple rule to follow is to pre pare a resin having atleast three phenolic nuclei and being organic solvent-soluble.Oxyethylate such resin, usin the following four ratios of moles ofethylene oxide per phenolic unit equivalent: 2t0 1; 6 to 1; l0to 1; and15 to 1. Fromasample '1 of each product remove any solvent that may bepresent, such as xylene. Prepare 0.5% and 5.0% solutions in distilledwater, as previously indicated. A mere examination of such series willgenerally reveal an approximate range of minimum hydrophile character,moderate hydrophile character, and maximum hydrophile character. If the2 to 1 ratio does not show minimum hydrophile character by test of thesolvent-free prodnot, then one should test its capacity to form anemulsion when admixed with xylene or other insoluble solvent. If neithertest shows the required minimum hydrophile property, repetition using 2to 4. moles per phenolic nucleus will serve. Moderate hydrophilecharacter should be shown by either the {i to l or 10 to 1 ratio, Suchmoderate hydrophile character is indicated by the fact that the sol indistilled water within the previously mentioned concentration range is apermanent translucent sol when viewed in a comparatively thin layer, forinstance the depth of a test tube. Ultimate hydrophile character isusually shown at the 15 to 1 ratio test in that adding a small amount ofan insoluble solvent, for instance 5% of xylene, yields a product whichwill give, at least temporarily, a transparent or translucent sol of thekind just described. The formation of a permanent foam, when a 0.5% to5.0% aqueous solution is shaken. is an excellent test for surfaceactivity. Previous reference has been made to the fact that otheroxyalkylating agents may require the use of increased amounts ofalkylene oxide. .However, if one does not even care to go to the troubleof calculating molecular weights, one can simply arbitrarily preparecompounds containing ethylene oxide equivalent to about 50% to 75% byweight, for example 65% by weight, of the resin to be oxyethylated; asecond example using approximately 200% to 300% by weight, and a thirdexample using about 500% to 750% by weight, to explore the rangeof'hydrophile-hydrophobe balance.

A practical examination of the f-actorof oxyalkylation level can be madeby a very simple test using a pilot plant autoclave having a capacity ofabout to gallons as'hereinafter described.

Such laboratory-prepared routine compounds can then be tested forsolubility and, generally speaking, this is all that is required to givea suitable variety covering the hydrophile-hydrophobe range. All thesetests, as stated, are intended to be routine tests and nothing more.They are intended to teach a person, even though unskilled inoxyethylation or oxyalkylation, how to prepare in a perfectly arbitrarymanner, a series of compounds illustrating the hydrophile-hydrophobestantially the same position as if one had personally made the resinprior to oxyethylation.

For instance, the molecular weight. of the internal structural units ofthe resinof the following over-simplified formula:

OH OH OH Hr e R R n R (nz'l to 13, or even more) is given approximatelyby the formula: (Mol. Wt. of phenol 2) plus mol. wt. of methylene orsubstituted methylene radical. The molecular weight of the resin wouldbe 11. times the value for the internal limit plus the values for theterminal units. The left-hand terminal unit of the above structuralformula, it will be seen, is identical with the recurring internal unitexcept that it has one extra hydrogen. The right-hand termi- 14 119.1unit lacks themethylene bridge element. Using one internal unit of aresin as the basic element, a resins molecular weight is givenapproximately by taking (n plus 2) times the weight of the internalelement. Where the resin molecule has only 3 phenolic nuclei as in thestructure shown, this calculation will be in error by several per cent;but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, theformula comes to be more than satisfactory. 'Using such an approximateweight, one need only introduce, for example, two molal weights ofethylene oxide or slightly more, per phenolic nucleus, to produce aproduct of minimal hydrophile character. Further oxyalkylation givesenhanced hydrophile character. Although we have prepared and tested alarge number of oxyethylated products of the type described herein, wehave found no instance where the use of less than 2 moles of ethylene 0xide per phenolic nucleus gave desirable products.

Examples 1b through 18b and the tables which appear in columns 51through 56 of our said Patent 2,499,370 illustrate oxyalkylationproducts from resins which are useful as intermediates for producing theesterified products of the present invention, such examples giving exactand complete details for carrying out the oxyalkylation procedure.

The resins, prior to oxyalkylation, vary from tacky, viscousliquids tohard, high-melting solids. Their color varies from a light yellowthrough amber, to a deep red or even almost black. In the manufacture ofresins, particularly hard resins, as the reaction progresses thereaction mass frequently goes through a liquid state to a sub. resinousor semi-resinous state, often characterized by being tacky or sticky, toa final complete resin. As the resin is subjected to oxyalkylation;

these same physical changes tend to take place in reverse. If one startswith a solid resin, oxyalkylation tends to make it tacky orsemi-resinous and further oxyalkylation makes the tackiness disappearand changes the product to a liquid. Thus, as the resin is oxyalkylatedit decreases in viscosity, that is, becomes more liquid or changes froma solid to a liquid, particularly when it is converted to thewater-dispersible or water-soluble stage. The color of the oxyalkylatedderivative is usually considerably lighter than the original productfrom which it is made, varying from a pale straw color to an amber orreddish amber. The viscosity usually varies from that of an oil, likecastor oil, to that of a thick viscous sirup. Some products are waxy.The presence of a solvent, such as 15% xylene or the like, thins theviscosity considerably and also reduces the color in dilution. No unduesignificance need be attached to the color for the reason that if thesame compound is prepared in glass and in iron, the latter usually hassomewhat darker color. If the resins are prepared as customarilyemployed in varnish resin manufacture, i. e., a procedure that excludesthe'presence of oxygen during the resinification and subsequent coolingof the resin, then of course the initial resin is much lighter in color.We have employed some resins which initially are almost water-white andalso yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to add, and we havepreviously pointed out that this can be pre-determined using laboratorytests, it is our actual preference from a practical standpoint to maketests on a small pilot plant scale. Our reason for so doing is that wemake one run, and only one, and that we have a commete series whichshows he pr gress ve effect f introducing the oxyalkyl ing agent, forinstance, the ethyleneoxy radicals. our preferred procedure is asfollows: We prepare a suitable resin, or for that matter, purchase it inthe open market. We employ 8 pounds of resin and 4 pounds of xylene andplace the resin and xylene in a suitable autoclave with an open refluxcondenser. We prefer to heat and stir until the solotion is complete. Wehave pointed out that soft resins which are fluid or semi-fluid can bereadily prepared in various ways, such as the use of orthoetertiaryamylphenol, ortho-hydroxydiphenyl, ortho-decylphenol, or by the useof-highor molecular weight aldehydes than formaldehyde. If such resinsare used, a solvent need not be added but may be added as a matter ofconvenience or for comparison, if desired. We then add a catalyst, forinstance, 2% of caustic soda, in the form of a to 30% solution, andremove the water of solution of formation. We then shut off the refluxcondenser and use the equipment as an autoclave only, and oxyethylateuntil a total of 60 pounds of ethylene oxide have been added, equivalentto 750% of the original resin. We prefer a temperature of about 150 C.to 175 C. We also take samples at intermediate points as indicated inthe following table:

Percentages Oxyethylation to 750% can usually be completed within 30hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to ounces, so thatno correction need be made in regard to the residual reaction mass. Eachsample is divided in two. One-half the sample is placed in anevaporating dish on the steam bath overnight so as to eliminate thexylene. Then 1.5% solutions are prepared from both series of samples, i.e., the series with xylene pr sent and. the series wi h Xyle e r moveMeie visual examination of any samples in soluti n may be suificient toindicate hyd phile character or surface activity, i. e., the product issoluble, forming a colloidal sol. or e aqueou sol ion f ms or showsemulsifying pr perty. All these properties are related throughadsorption at the interface, for example, a gasaliquid in erface or aliquid l qu interface. If desired. surface activity can be measured inany one of the usual ways using a Du Nouy tensiometer or droppin p pe tor any o her procedure for measuring interfacial tension. Such tests areconventional and require no further description. Any compound havingsub-surface-activity, and all derived from the same resin andoxyalhylated to a greater extent, 1. e., those having a greaterproportion of alkylene oxide, are useful for the practice of thisinvention.

Another reason why we prefer to use a pilot plant test of the kind abovedescribed is that we can use the same procedure to evaluate tolerancetowards a trifunctional phenol such as hydroxybenzene or inetacresolsatisiactorily. Previous reference b en made to th fact tha on canconduct a laboratory scale test. which will indioate whether or not aresin, although soluble in solvent, will yield an insoluble rubberyproduct, i. e., a product which is neither hydrophile norsurface-active, upon oxyethylation, particularly extensiveoxyethylation. It is also obvious that one may have a solvent-solubleresin derived from a mixture of phenols having present 1% or 2% of atrifunctional phenol which will result in an insoluble rubber at theultimate stages of oxyethylation but not in the earlier stages. In otherwords, with resins from some such phenols, addition of 2 or 3 moles ofthe oxyalkylating agent per phenolic nucleus, particularly ethyleneoxide, gives a surface-active product which is perfectly satisfactory,while more extensive oxyethylation yields an insoluble rubber, that is,an unsuitable product. It is obvious that this present procedure ofevaluating trifunctional phenol tolerance is more suitable than theprevious procedure.

It may be well to call attention to one result which may be noted in along drawn-out oxyalkylation, articularly oxyethylation, which would notappear in a normally conducted reaction. Reference has been made tocross-linking and its effect on solubility and also the fact that, itcarried far enough, it causes incipientstr nsiness, then pronounc dstrinsine usua ly followed by a semhrubbery or rubbery stage. Incipientstringmes .v or even pronounced stringiness. or even the end ncy towarda rubbery stage, is not objectionable so long as the final product is stl hydr ohil and at least surface active. Such material frequently isbest mixed with a polar solvent, such as alcohol or the like, andpreferably an alcoholic solution is used. The point. which we want tomake here, however. is this: Stringiness or rubberization at this stagemay possibly be the result of etherification. Obviously if adifunctional phenol and an aldehyde produce a non-cross-linked resinmolecule and if such molecule is oxyalkylated so as to introduce aplurality of hydroxyl groups in each molecule, then and in that event ifsubsequent etherification takes place, one is going to obtaincrosslinking in th same general way that one would obtain cross-linkingin other resinification reactions. Ordinarily there is little or notendency toward etherification during the oxyalkylation step. If it doestake place at all, it is only to an i si nificant and nd tectable d gre. H w ver. suppose that a certain Weight of resin is treated with anqual we t of. r t i e its i t of. ethylene oxide. This may be done in acomparatively short time, for instance, at or C. in 4 to 8 hours, oreven less. On the other hand. if in an exploratory reaction, such as thekind previously described, the ethylene oxide were added extremelyslowly in order to take stepwise samples, so that the reaction required4 or 5 times as long to introduce an equal amount of ethylene oxideemploying the same temperature, then etherification might causestringiness or a suggestion of rubberiness. For this reason if in anexploratory experiment of the kind previously described there appears tobe any stringiness or rubberiness, it may be well to repeat theexperiment and reach the intermediate stage of oxye allrylation asrapidly as possible and then proceed slowly beyond this intermediatestage. The enthe purpose of this modified procedure is to cut down thetime of reaction so as to avoid etherification if it be caused by theextended time period.

it may. be well to note one peculiar reaction sometimesnoted in thecourse of oxyalkylation, particularly.oxylethylation, of thethermoplastic resins herein described. This efiect is noted in a casewhere a thermoplastic resin has been oxyalkylated, for instance,oxyethylated,. until it gives a perfectly clear solution, even in thepresence of some accompanying water-insoluble solvent such as to ofxylene. Further oxyalkylation, particularly oxyethylation, may thenyield a product which, instead of giving a clear solution as previously,gives a very milky solution suggesting that some marked change has takenplace. One explanation of the above change is that the structural unitindicated in the following way where 8n is a fairly large number, forinstance, 10 to 20, decomposes and an oxyalkylated resin representing alower degree of oxyethylation and a less soluble one, is generated and acyclic polymer of ethylene oxide is produced, indicated thus:

This fact, of course, presents no difiiculty for the reason thatoxyalkylation can be conducted in each instance stepwise, or at agradual rate, and samples taken at short intervals so as to arrive at apoint where optimum surface activity or hydrophile character is obtainedif desired; for products for use in'the'practice of this invention, thisis not necessary and, in fact, may be undesirable, i. e., reduce theefiiciency of the product.

We do not know to What extent oxyalkylation produces uniformdistribution in regard to phenolic hydroxyls present in the resinmolecule. In some instances, of course, such distribution can not beuniform for the reason that we have not specified that the molecules ofethylene oxide, for example, be added in multiples of the units presentin the resin molecule. This may be illustrated in the following manner;1

Suppose the resin happens to have live phenolic nuclei. If a minimum oftwo moles of ethylene oxide per phenolic nucleus are added, this wouldmean an addition of 10 moles of ethylene oxide, but suppose that oneadded 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously,even assuming the most uniform distribution possible, some of thepolyethyleneoxy radicals would contain 3 ethyleneoxy units and somewould contain 2. Therefore, it is impossible to specify uni:- formdistribution in regard to the entrance of the ethylene oxide or otheroxyalkylating agent. For that matter, if one were to introduce 25 molesof ethylene oxide there is no way to be certain that all chains wouldhave 5 units; there might be some having, for example, 4 and 6 units,orforthat matter 3 or 7 units. Nor is there any basis'for assuming thatthe number of molecules of the oxyalkylating agent added to eaeh of themolecules ofthe resin is the same, or different. Thus, where formulaeare given toillustrateor 18 depict the oxyalkylated products,distributions of radicals indicated are to be statistically taken. Wehave, however, included specific, directions and specificationsin regardto. the total amount of ethylene oxide,-or-total amount of any otheroxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylatedcompounds; andfor that matter derivatives. of, the. latter, the following should benoted; In oxyalkylation, any solvent employed should be non-reactive,tothe alkylene oxide employed. x'Ihis. limitation does notapply to'solvents usedin cryoscopic determinations for obvious reasons. ..Attentionis directed to the fact that various organic solvents may be employed toverify that the resin is organic solvent-soluble. Such solubility testmerely characterizes the resin. The particularv solvent used in suchtest may not be suitable for a. molecular weight determination and,likewise,- the solvent used in determining molecular weight may not be.suitable as a solvent. during oxyalkylation; For solution of theoxyalkylated. compounds, or their derivatives a great variety ofsolvents may be, employed, such as alcohols, ether. alcohols, cresols,phenols, ketones, esters, etc., alone or with the additionof water. Someoftheseare mentioned hereafter. Weprefer the use ofbenzene or.diphenylamine as a solventin making cryoscopic measurements. The mostsatisfactory resins are those which are solublein xylene. or the like,rather than those which are soluble only in some other solventcontaining elements other than carbon and hydrogen, for. instance,oxygen or chlorine. ,Such solvents are usually .polar, semi-polar, orslightly polar ,in nature compared withxylene, cymene, etc.,

Reference to cryoscopic measurement is concernedwiththe use of benzeneor other suitable compoundas a solvent. Such method willshow thatconventional resins obtained, for example, from para-tertiary,amylphenol and..formaldehyde in .presenceof an acid catalyst, will. havea molecular weight indicating 3,4, 5. or somewhat greater number ofstructuralunits per molecule. Ifnlore drastic. conditions ofresiniI-lcation are employed or, if suchlow-stage resin is subjected to,a ..vacuumv distillation treatment A as previously described, oneobtainsa, resin .of. a. distinctly higher, molecular weight. Anymolecular. weight determination. used, whether cryoscopic meas:

urement -.or, otherwise, otherv than the conventional, .cryoscopic .oneemploying benzene, should be checkedsoasto insure that itgivesconsistent values on such conventional resinsas .a control. F equentlyall that is necessary to make. an approximation of .themolecular weightrange is to makea comparison with the dimer obtained by chemicalcombination of two moles of they same phenol, and, one moleof the samealdehyde.under ..conditions, to. insure dimerization. ..As to thepreparation of suchdimers from substituted phe-. nols, seeCarswell,Phenoplastsf? page 31.. The increased. viscosity, resinous. character,and decreased solubility, etc., of the. higher polymers incomparison-With the dimer, frequently areall that is. required. ..toestablish that the resin contains 3 ormorestructural per molecule.

Ordinarily, the ,oxyalkylation is carried out in autoclaves providedwith. agitators. or. stirring devices. We. have found that, thespeed ofthe agi: tation markedl influences thetime reaction. .In some .cases, 5the change. from slow speed aeita: tion, for. example, in..a-.laboratoryautoclave agitation. .with a. stirrer. operating at a speed of 60 to200R. P.'M., to high speed agitation, "with the stirrer operating at 250120350 :R. .P. :M., reduces the time required for oxyalkylation by aboutonehalf to two-thirds. Frequently xylene-soluble products which giveinsoluble products by .procedures employing comparatively slow speedagitation, give suitable hydrophile products when produced by simliarprocedure but with high speed agitation, as a result, we believe, of thereduction in the time required with consequent elimination orcurtailment of opportunity for curing or etherization. Even if theformation of an insoluble product is not involved, it .is irequentlyadvantageous to speed up the reaction, thereby reducing production time,by increasing agitating speed. in large scale operations, we havedemonstrated that :economical manufacturing results from continuousoxyalkylation, that is, an -operation in which the-alkylene oxide :iscontinuously fed :to the reaction vessel, with high speed agitation, 'i.e., an agi'tator operating at 250 to 350 R. Continuous ioxyalkylation,other conditions :being the same, is "more rapid than batchoxyallcy-lation, but :the latter is ordinarily more convenient forlaboratory-operation.

Prwious reference has beenimade to the fact that in preparing estersorpompoundsof:the kind herein described, particularly adaptedioridemulsification of water-in-oibemulsions, and 'for that matterion-other purposes, 'one'should make a complete exploration of the widevariation in hydrophobe-hydrophile balance :as previously referred to.It has been stated, furthermore, that this hydrophobe-hydrophfle balanceof the oxyalkylated resins is imparted, :as far as the range ofvariation goes, to a greater or lesser-extent to the herein describedderivatives. This means that one employing the present invention-shouldtake the :choice of the most suitable derivative selected from a numberor" representative compounds, thus, inot only should avariety of resinsbe prepared exhibiting .a variety of oxyalkylations, particularlyoxyethylations, but also a variety of derivatives. can be :done -conveniently inlight'of what has been said previously. From :a practicalstandpoint, :using pilot plant equipment, for instance, an autoclavehavinga capacity of approximately three to five gallons. We have made asingle run by appropriate' selections in whichthe molal ratio'o'f :resinequivalent to ethylene oxide iis -one to one, i to 5, il tol0, =1:-to'15,:and 1110 20. Furthermore, in making these particular runs we haveused -continuous addition oi ethylene oxide. the :continuous addition oiethylene oxide we have employed either a cylinder of ethylene oxidewithout added nitrogen, providedthatthe pressureof the ethylene oxide:was sufficiently great to pass into the autoclave, :or else we haveused an arrangement which, :in essence, was :the equivalent of anethylene oxide cylinder with a means for injecting nitrogenso as to:force out the ethylene oxide in the manner ot-an ordinary seltzerbottle, combined with the .means .i or either weighin the cylinder ormeasuring the ethylene oxide :used volumetrieally. Such procedure andarrangement for injecting liquids is, of course, conventional. Thefollowing data sheets exemplify such operations, i. e., :the combinationof both continuous agitation and taking samples so as to give five:different variants oxyethylation. In adding ethylene oxideucontinuously, there is one precaution which :must be'taken atall times.The addition of ethylene oxide must stop immediately if 'therelisianyindication that reaction is stopped or, obviously, if reaction isnotstarted at :the 1-beginning of the reaction period. :Since1theadditionof ethylene oxideis invariably an exothermic reaction, whether ornotreactionhasitakenplace can be judged in .the usual :manner by observin(a) temperature :rise .or drop, .if any, Llb) amount of cooling water orother means required to-ldissipate heat of reaction; thus, if there .atemperature drop without the use of cooling water or equivalent, or ifthere .is no rise in temperature without usingeooling water control,icareiul investigation should be made.

.In .the .tables immediately following, xwe .are showin the maximumtemperature and "usually the operating temperature. In other words, :byexperience we :have iound'that if the initial ireactants are-raised tothe indicated temperature and then .if ethylene :oxide is added slowly,this .temperature is maintained by cooling water :until theloxyethylation is icomplete. We have .also in" dicated the maximumpressure that we obtained or the pressure range. Likewise, we haveindicated the time required to inject the ethylene oxide as well as abrief note as to the solubility of the product at the end of theoxyethylation period. As one periodends it will be noted we have removedpart of the oxyethylatedmass to give us derivatives, as thereindescribed; the rest has been subjected to further treatment. All this isapparent by examining the columns headed ZStarting mix, Mix at end ofreaction, Mix which is removed for sample, and Mix which remains as nextstarter.

The resins employed are prepared in the manner described in Examples 1athrough 103a of our .said .Patent' 2,499,370, except that instead ofbeing prepared on .a laboratory scale they were prepared in .10 to l5-ga1l0n electro-vapor heated synthetic resin pilot plant reactors, asmanufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their Bulletin No. 2087 issued in .1947, withspecific reference to Specification No. 771-3955.

For convenience, the following tables give the numbers of the examplesof our said Patent 2,499,370 in which the preparation of identicalresins on labora ory s ale are described. it is understood thatin the.iollowing examples, the change is one with respect .to the .size of theoperation.

The :solvent .used .in each instance was xylene. This solventparticularly satisfactory for the reason that it can :beremoved readilyby distillation orvacuum distillation. :In-these continuous experimentsthe speed of the stirrer in=the autoclave was*250 R.':P. 'M.

In/examining the subsequent tables it W-ill be noted that ii acomparatively small sample "is taken at eaohstage, or instance, /2 toone gallon, one can proceed through the entire -mo1a-l stage of -1 to*1, to -1 to 20, without-remaking at any intermediate stage. This isillustrated by Example 104a. In other examples we -found .i't desirableto take a larger sample, for "instance, a 3-ga3llon sample, at anintermediate stage. As a result it was necessary in such instancestostart with a new resin-sample -in-order-toprepare sulficlentoxyet-hylatedderivatives illustrating'thelatter'stages. Under*suchcircumstances, of course, the earlier stages which had beenpreviously prepared -were by-passed or ignored. This is illustrated inthe tables where, obviously, it shows that the starting mix was notremoved Troxri a previous-sample;

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin:Formaldehyde Date [Resin made in pilot plant size batch, approximately25 pounds, corresponding to 3a of Patent 2,499,370 but this batchdesignated 1040.]

f Mix Whleh'ls Mix Which Re- Starting Mix Egg of Removed for. mains asNext ac Sample Starter M8x Max Time Pressure, Temp erahrs. SolubilityIslbls. abs. Lbs lslbls. gbs. Lbs lslbls. ns. lslbls. gas.

o eso eses- 0 es- V vent in Eto vent in Eto vent in Eto vent in E FirstStage Resin to Et0 M01211 Ratio 1:1 14.25 15.75 0 14.25 15.75 4.0 3.353.65 1.0 10.9 12.1 3.0 80 150 M I Ex. No. 1045.....

Second Stage Resin to EtO.. Molal Ratio 1:5 9 12.1 3.0 10.9 12.1 15.253.77 4.17 5.31 7.13 7.93 9.94 70 158 $4 ST Ex. No. 1055..-;

Third Stage Resin to EtO. Molal Ratio 1: 7 13 7.93 9.94 7.13 7.93 19.693.29 3.68 9.04 3.84 4.25 10.05 00 173 )5 "FS Ex. No. 1065"-.-

Fourth Stage Resin to EtO 1 Molal Ratio 1:15.}3 84 4.25 10.65 3.84 4.2516.15 2.04 2.21 8.55 1.80 2.04 7.60 220 100 -RS Ex. No. 107b Fifth StageResin to Et0 1 Molal Ratio 1:20 1.80 2.04 7.60 1.80 2.04 10.2 100 150 $6QB Ex. No. l08b.

I=Insoluble. BT= Slight tendency toward becoming soluble. FS=Falrlysoluble. RS= Readily soluble. QB: Quite soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date v Vv [Resin made in pilot plant size batch, approximately pounds,corresponding to a of Patent 2,499,370 but this betch designated 109a]Mix Which Is -Mix Which Re- Starting Mix fig fi g of Removed for mainsas Next Sample Starter Max. Max. Tim I Pressure, Temp erahm Solubilitylslbls. abs. Lbs Ibls. fibs. Lbs gbls. I bs; Lbs Islbis. 55. 9

oes- 0- es- 0- es 0- esvent in Eto vent in Eto vent in Eto vent in EtoFirst Stage ResintoEt0 v r e e Molal Ratio 1'1 15 0 15.0 0 15.0 15.0 35.0 5.0 1.0 10.0 10.0 2.0 50 150 1% ST Ex. No. 1095.....

Second Stage Resin to Et0 Molal Ratio 1:5 10 10 2 0 10 10 9 4 2 72 2 722 56 7.27 7 27 6 86 147 2 D'I Ex. No.110b

Third Stage n b o U. V 1. Molal Ratio 1: 10-. 7 27 7. 27 6.86 7. 27 7.2713.7 4.16 4.16 7.68 3.15 3.15 5.95 1% 8 Ex. No. 1115.....

Fourth Stage ResintoEtO Molal Ratio1:15 3.15 3.15 5. 95 3.15 3.15 8.951.05 1.05 2.95 2.10 2.10 6.00 220 174 2% S Ex. No. 112b Fifth StageResintoEtO -I 1 Molal Ratio1:20 2.10 2.10 6.00 2.10 2.10 8.00 220 183 36VS Ex. N0. 113b- S=Soluble. ST=S1ighttendencytowerd solubility.DT==Deflnlte tendency toward solubility. ts verysolnble.

Phenol for resin: Paraoc'tylphenol Aldehyde for resin: Formaldehyde Date[Resin made iii pilot plant size batch, approximately pounds,corresponding to 8a 01 Patent 2,499,370 but this batch designated 114mlMix Which Is Mix Which Re- Starting Mix i gg ggg of Removed for mains asNext Sample Starter Max. MBA. Tim v I Pressure. Temp erm Solubility Lbs.Lbs. Lbs Lbs. Lbs. Lbs. Lbs. Lbs Lbs. Lbs. Sdl- Res- Sol- Res- Sol Res-801- Resvent in vent in went in vent in First Stage Resin to EtO MolaiRatio 1 14.2 15.8 0 14.2 15.8 3.25 3.1 3.4 0.75 11.1 12.4 2.5 150 1542NS Ex. No. 1X45--.

Second Stage Resin to 10120.... Molal Ratio 1:5 11. 1 12.4 2.5 11.1 112.4 12.5 7.0 7.82 7.88 4.1 4. 58 4. 62 171 $6 SS Ex. No. 1155..- 1

Third Stage Resin to EtO. Molal Ratio 1:10.- 6. 64 7.36 0 6.64 7. 3515.0 s. 190 1% S Ex. N0. 1165..."

Fourth Stage Resin to EtO.. M0181 Rati01:15 4.40 4.9 0 4.4 4.9 14.8 400160 $4 VS Ex. N0. 1170.-.

Fifth Stage Resinto Et0 Molal Ratio 1:20.- 4.1- 4. 58 4.6 4.1 l. 4. 58-18.52 250 172 '95 VS Ex.N0.118b

S=Soh1ble. NS=Not'solub1e. SS Somewhat soluble. VS=Very soluble.

Phenol for resin: M enthylphenol Aldehyde for resin; Formaldehyde Date[Resin made in pilot plant size batch, approximately 25 pounds,corresponding to 69a of Patent 2,499,370 but this batch designated 119a]Mix Which 19 Mix Which Re- Starting Mix fig' ggg of Removed for mains asNext Sample Starter Max. Max.- Time 7 Pressu e, Temp erahrs. SolubilityLbs. Lbs.- Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs S01- Res 801-Res- Sol- Res- Sol- Besvent in vent in vent in vent; in

First Stage Resin to EtO. M01211 Ratio 1:1-.- 13. 65 16.35 0 13. 65 16.35 3.0 9.55 11.45 2.1 4. 1 4.9 0.9 60 1% NS Ex. No. 1195.... 7

Second Stage Resin to EtO M0181 Ratio 1:5..- 10 12 0 10 12 10.75 4.525.42 4.81 5. 48 6.58 5.94 140 100 1542 S Ex.No.120b

Third Stage Resin to EtO-.-. Molal Ratio 1:10-- 5.48 6.58 5. 94 5.486.58 10.85 90 M. S EX. N0. 1210...

Fourtli Stage Resin to EtO- M0181 Ratio 1:15 4.1 4.9 0.9 4.1 4.9 13.15180 171 1%: VS Ex. N0. 1220.....

Fifth Stage Resin b0 EtO M0131 Ratio 1: 0.- 3.10 3.72 0.68 3.10 3. 7213.43 320 VS Ex. No. 123b--.-.

S== Soluble. NS=Not soluble. VS= Very soluble.

Date

Aldehyde for rest'n: Formaldehyde [Resin made in pilot plant size batch,approximately 25 pounds, corresponding to 20 of Patent 2,499,370 butthis batch designated 12441.1

. Mix Which is Mix Whieh Re- Starting Mix fig figg of Removed for mainsas Next Sample Starter.

Max. Max. Time Pressure, Temperahm Solubility 1 .1. 5. kbs. gbls. Ifibs.Lbs gbls. Ifibs. Lbs I m bs.

o eso eso eso esvent in Etc vent in Eto vent in E to vent in Eto FirstStage ResintoEt0 x i Molal Ratio 1:1 14. 15.55 0 14.45 15.55 4.25 5.976.38 1.75 8. 48 9.17 2.50 5 150 M2 ;NS 9 Ex. N0. 1240-. '1

Second Stage Resin to Et0 v p y I M0151 Ratio 1:5 8.48 9. 17 2.50 8.489.17 16.0 5.83 6.32 11.05 2. 2.85 4.95 95 188 M SS Ex. N0. 125b.

Third Stage ResintoEt0-- M0131 Ratio 1:10.. 4. 82 5. l8 0 4. 82 5. 1814. 25 400 183 M B Ex. No. 12612..

Fourth Stage Resin to Et0 M0181 Ratio 1:15.. 3. 4. 15 0 3.85 4. 15 17. 0e 120 180 $5 VS Ex. N0. 1270- Fifth Stage Resin to 15150.... x I V M0181Ratio 1:20.. 2. 65 2.85 4. 2. 65 2. 85 15. 45 80 170 Ha I I VS Ex. N0.128b r S=Solub1e. N S=Not soluble. SS=Somewhat soluble. VS Very soluble.

Phenol for resin: M enthyl Aldehyde for'resin': Propionalde'hyde Date{Resin made on pilot plant size batch, approximately 25 pounds,corresponding to 81a of Patent 2,499,370 but this batch designated1290.]

Mix Which is Mix Which Re- Starting Mix figg gg of Removed for mains asNext Sample Starter Max. Max. Time Pressure,- Temperahm Solubility 1 .1.5. libs. Lbq Ibls. 115. Lbs Ibls. fibs. Lbs 1 .13 5. abs. Lbs

O- es- 0- ES- 0- es- 0- e5- vent in Eto vent in Eto vent in Eto vent inEto First Stage Resin to Et0 Molal Ratio 1:1 12.8 17. 2 12. 8 17. 2 2.75 4. 25 5. 7 0. 95 8. 65 11. 50 1. 80 110 150 16 Not soluble. Ex. No.12911--." I I Second Stage Resin to EtO.-. Molal Ratio 1: 8; 55 11.501.80 8. 55 11. 50 9.3 4. 78 6.42 6. 2 3. 77 5.08 4.10 100 170 $6Somewhat Ex. No. b e soluble.

Third Stage Resin to EtO. Molal Ratio 1:10-. 3. 77 5. 08 4. 10 3. 77 5.08 13.1 100 182 $42 Soluble. Ex. No. 1310.....

Fourth Stage Resinto EtO Molal Ratio 1 :15 5. 2 7. 0 5. 2 7.0 17. 0 2.10 2. 83 6.87 200 182 M Very soluble. Ex. No. 1325..... v

Fifth Stage Resin to EtO.. I Molal Ratio 1: 2. 10 2. 83 6. 87 2. 10 2.83 9.12 90 $6 Do., Ex. No.138b- Phenqbj r resin: Famfiz'r iM-yamylp'henol;

Aldehyd6-forresin: Furfuml:

Date

[Resinmade an pil kn antnizebfitcli. ppyoxi inajely-zfi pounds,cgrresppnding 42.; of -Pate nt.:2,499;37O bummshamh designated 213134;]

Y c Mix Whichis Mix Which Re- Starting figg ggg I Removed-jurmainsasNeggt Sample Starter Max. Max. Time ifiressuge, gempya- Solubility Lbs.Lbs. "Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. i Lbs. Lbs. 'Lbs. I 1 Lbs. 801- Res-S01- -Bgs-. Spl- Bes- S q1- 39 vent in Eto vent in vent, in Eto went inEto First Stage.

Resinto EtO Molal Ratiol 11.2; 18.0 11.2 ;1 8 .0 3;.5 2.75 4.4 1 0.858.45.13.6 2.66. 120 1.35; My NohsOluble. Ex. N0. 184b.

Second Stage Resin to EtO MolalRatiol'fi 8.45 13.6 2.65 84513.6 112.65;5.03. 8.12; 7,55: 3.42 5.48 5.10 110 150 M Somewhat Ex. No. 1351;..."soluble.

Third Staaq;

Resinto Et0. M0181 Ratiol-ID. 4 .5; 8.0 4.5 8.0; 14. 5 2. 4 5.35 7.902.0.5 3065: 6.60 180 firstflpbl'e. Ex. No. 13617..

Fourth Stage Resinto EtO MolalzRatiol Q 3,142 5. 48 5.10 3.42 5.43 15.10180 188 ;verysoluble. Ex. No. 1370"...

Fifth Stage.

Resin to 15110.... Mo1al.Ratlo1:29 2.05 3.65 6.60 2.06 3 6 5 133,35, 120125 34; Do. Ex. No. 1138b..... 1

Phenol for I resin M Zmthyl.

Aldehyde for resin: Eurfuml" Date [Resin made on pilot sizebatch,approximately pounds; corresponding-to-89a of Patent 2,499,370buvthisbateh designated as1'39|z.]

Mix Which is- Mix Which-Be; Starting Mix g g Removed tor mains as, Ne xtSample Starter Max. Max. Time Pressure, Tempsmhrs. Solubility 1 5. libs.Lbs lbls. p Lbs l b s. I b s. lbls. ps. Lbs tum f 0- esoe s-y ooe s-.vnt in Eto vent; in Etc Went in vent in First Stage.

Resinto EtO. MolaLRatio 10.25 1?. 75 10.25 17.75 25. 2.65 4.60 0. 7:613.15 1.85 90- 150 1'6 7 N01 Ex. N0. 139b soluble.

Second Stag;

Resin to E20 Molal Ratio 1'5 7. 6* 13.15 1.85 7.6 13.15 9:35 5.2 9.006.40 2;4 4.15 2.95 I S0 177 $6 1 Somewhat Ex. N01 1406... soluble.

Third Slav Resln tq EtQ. Mela] Ratiol A 4.22 6.98 4.22- 69810.0 0--.. 901 $4 Spluble. Ex. N0. 1411).

Fourth Stag;

Rgsin to EtQ. I MolalRatiolzlfifl 3.76 6. 24 3.7 i 6.24 13. 25 100 417-1 l Very; Ex. No. 142b soluble.

Fifth Stage;

Resin to E t0 Mola1Ratio1z20- 2:4 4.15 2. 95 2.4 4.15 1-1- 1'60 )4: Do,Ex. No. 1431;.

Date

[Resin made on pilot plant size bateh, 'approximat para-octylphenolrep1acing164 pa Phenol for resin: "Para-octyl Aldehyde j'ornsinf Fuifural i Mix Which is I Mix Whicli Rs- Starting Mix figg g of Removed Tormains as Next j w Sample Starter MEL I q v Pressure, Tempsras 1L3?Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. 4 Sol- Res- Egg- Bol-Resg g' Res: E1 801- Resfigvent in .vent in .vent in. L vent in FirstStage ResintoEt'0 v v I M0181 Ratio 131." 12. 1 l8. 6 12. 1 18. 6 3. 05. 38 8. 28 l. 34 6. 72 10. 32 1. 66 80 150 H: Insoluble. Ex. No.1440..-

Second Stage I Slight tend Resinto EtO- ency to- MOIBI Ratio 1:5". 9.14. 25 9. 25 14. 25 11. O 3. 73 5. 73 4. 44 5. 52 B. 52 6. 56 100 177 K:ward be- Ex.No.145b coming soluble Third Stage Resinto-Et0 E a M0131R8110 1:10 6. 72 10. 32 l. 66 6. 72 10. 32 14. 91 4. 97 7. 62 11. O1 1.75 2. 3. 90 85 182 $4 Fairly SOIIP Ex. No. 146b I v e.

Fourth Stage Resinto.Et0 r Moial RBfiO 1:15.. 5. 52 8. 52 6. 56 5. 52 8.52 19. 81 100 176 $4 Readilysolu- Ex. No. 147b- I ble.

Fifth Stage ResintoEtouu f M0181 B81510 1220 1. 2. 70 3. 90 1. 75 2. 708. 4 160 M Quite S0111- Ex. N0. 14 8b.. I ble. 7

' Phenol for i'esin: Para-phenyl Aldehyde f0? 7min Furfaral Date [Resinmade on pilot plant size batch, approximately 25 pounds paraphenylphenolreplacing 164 parts by welgh corresponding to 420 0! Patent 2,499,370with 170 parts by weight of commei'eial t of para-tertiary amylphenolbut this batch designated as 1490.]

Mix Which 1". Mix Which Re- Starting Mix figg figg of Removed for mainsas,Next

Sample Starter Max V 'Pre'ssure, Tempgerag f Solubility Lbs. Lbs. Lbs.Lbs. Lbs. Lbs.- Lbs. Lbs. Sol- Res- Res- Sol- Res- Sol- Resvent in 'Etovent in Eto vent in Eto vent in Eto First Stage ilesintofitdnu V I vMolal Ratio 1:1..- 13.9 10.7 13.9 10.7, 3.0 3.50 4. 25 0.80 10. as 12.462.20 100 100 $6 n oluble. Ex. No. 1490..;...

Se -0nd Stage Resin to 210-... 1 911 111 iei ia- Molal Ratio 1:5..-10.35 12. 45 2.20 10.35 12. 45 12.20 5.15 6.19 6.06 5.20 6.26 6.14 so183 is "3 Ex. No. 1500..... I 0

bihty. Third Stage iissinm 1:10-.-- M0181 Ratio 1'10 8.90 10.7 8.9010.70 19.0 5.30 6.38 11.32 3.60 4.32 7.68 193 M2 Fairly 50111- Ex. No.151b ble. 1

Fourth Stage Resinto EtO Mole] Ratio 1:1 5.20 6.26 6.14 5.20 6.26 16.64171 Read1ly sol- Ex. No. 1520-- uble.

Fifth Stage Bes1iii011t0... h

Sample somewhat rubbery and gelaggg %g g j?? z} 1 4232.. tinousbutfairly soluble 230 2 mamas 31 32 Phenol for-resin-rPatm-seeondarymtmylphmol Aldehyde for resin: Furfural Date [Resin madam:pilot plantsize batch, approximately zfipounds, oorrespondingto 88a ofPatent2,499;370 butz this bstcix designatedaszlflml' Mix Which is MixWhich Re- Btarting Mix figg figg I Removedifou mainxaaNext 1 Sample 1Starter. Mam Mam Pressure, Tempsrag Solubility -.[s,bls; bS. Lbs fr b a.1 2s. 1 11 5. 'lgs. 1 b l bs. o esv V osbesv vent in Etc vent. in; Emvent vent; in

Fii'at Stake. Resin to EtO I M01211 Rati01:1 10.85 20.75 10.85 20.76 3.02.57 4.90 0.73 8.28 15.36 2.27 100 150 ,5 Iixsoluhlm Ex..NiL15,-1I2- 2'i 1 h Second Stage t. Resin tmEtQ--. tendency MolahB-atiolzfi.-. 8.2815.85 2.27 3.28 15.85 11.77 3.82 7.33 5.45 4.46 8.52 6.32 100 182 16t'oward: Ex. No. 1556..... i 1 1 i l f 1 5 becoming suiubl.

TMxdStage Resin to EtO-,... Mo1alRatio1:10. 5.95 11.35 A--. 6.95 11.3516.75 3.38 6.42 9.50 2.57 4.93 7.25 100 181 Failfly; Ex-..N0.156b'.-...1 3 3 E E 5 f soluble;

Fourth Stage 1 Resin to EtO Molal Batiolzlfi 4.46 8. 52 6.32 4.46 8. 5219. 07 188 M Readily- Ex..N,o:.L5Tl1. i 1' i so1ufi1m Fifth stage,

Resin to Et0 Molal Ratiol: 2 57 4.93 7.25 2.57 4.93 14.50 $6. Qu'ituEx..No..158(i 5 I soluble.v

Phenol for resin: Pqra-phenglphenol Aldehydefor resin: Formaldehyde Date[Resin made on pilot plant size batch, approximately 25 pounds,corresponding to Be 0! Patent 2,499,370 but this batch designated as159a,]

- ining p e: 1 Starter, Max Max.

' V I Pressutel pgrsfif" Solubility :Lbs 131s. iLbs. Lbs. Lbs: Lbs. Lbs.labs; Lbs. Lbs; -sq.m. g 0 .801: 23

SoI- R es- Ego Sol- R es- Etc) 501- Bile:- Eto Starting Mix vent m vnt111x vent m vent First Stage:

Resin to 12120-... Molal Ratio 1' Thitistaaeg e 1 I Fourtfiistage Resinto Et0 3 Molal Ratio 1:15.. Ex. No

Fiftfins'taqeg Resin to EtO...

Molal Ratio 1:20.. Ex. N0. 1600..."

2.80 3.64 3.41" 2.80 13.64 so nsoluble.

Phenol forresin: Pam-secondary butylphenol Aldehyde for resin: FurfuralDate [ Resin made on pilot plant size batch, approximately 25 pounds,corresponding to 42a of Patent 2,499,370 with 150 parts by weight ofcommercial para-secondary butylphenol replacing 164 parts by weight ofpara-tertiary amylphenol but this batch designated as 16111.]

. Mix Which is Mix Which Re- Starting Mix fi 53 Removed .ior mains asNext I Sample I Starter Max. Max I I I I I Pressure, Temgera- EE?Solubility lslbls. libs. Lbs lslbls. 135. l b s. r bs. I b s. gigs.

o eso eso eso esvent in Eto vent in I m vent I in I m vent in Eto FirstStage Resint0EtO. v 7 Molal Ratio 111.. 12 0 17.9 12.0 17. 9 3.5 2.653.98 0. 77 9.35 13.92 2.73 150 171 P6 InsolubloJ Ex. No. 16111"...

Second Stage Slight tend- Resin to EtO v enoy t0- Molal Ratio 1:5. 9 3513. 92 2. 73 9.35 13.92 13.23 5.00 7.42 7.08 4.35 6. 50 6. 15 100 192 36ward be- Ex. No. 16211.... coming soluble. Third Stage Resin to EtO. 1Molal Ratio 1:10. 6 8. 95 6. 25 8. 95 17.0 3. 23 4.61 8. 76 3.02 4.348.24 120 188 ,942 Fairly solu- Ex. No. 163b ble.

Fourth Stage Resinto EtO.- Molal Ratio 1:15. 4 36 6. 6. 15 4.35 6. 5018.40 100 181 is Readily sol- Ex. N0. 1640"-.. uble.

Fifth Stage Resin to EtO.-. Sample somewhat rubbery and gelat- I MolalRatio 1:20- 3 02 4.34 8.24 3.02 4.34 16.49 inous but shows limited watersol- 120 161 4 Ex. No. 16511.. ability. I I I Phenol for resin:Pam-octylph'enol Aldehyde for resin: Propio'naldehyde Date [Resin madeon pilot plant size batch, approximately 25 pounds, corresponding to3441 of Patent 2,499,370 with 206 parts by weight of commercialpara-octylphenol replacing 164 parts by weight of para-tertiaryamylphenol but this batch designated as 1660.]

I I Mix Which is Mix Which Re- Starting Mix figg fi g of Removed formains as Next 1 Sample Starter Max. Max. Time I I I Pressure, Temp erahmSolubility lbls. fibs. Lbs lslbls. gbs. tbs Islbls. gbs. Lbs l''bls.Ifibs. Lbs l o eso eso eso esvent in Eto vent .in vent in Eto vent inEto First Stage Resin to EtO 1 z v I I Molal Ratiol 13 3 16. 9 13.3 16.93. 0 3. 1 4.0 0. 10. 2 12.9 2.3 100 150 $6 Insoluble. EX. No. 16Gb.-.

Second Stage Resinto Et0-.. i Molal Ratio 1 5 10 2 12. 9 2.3 10. 2 12. 911.3 6.34 8.03 7. 03 3. 86 4.87 4. 27 100 166 M. B ecoming Ex. No. 167bsoluble.

Third Stage Resin to EtO v I I Molal Ratio l:11.3 6 46 8. 24 6. 46 8. 2416. 5 3. 52 4. 49 8. 99 2. 94 3. 7. 51 177 V4 Fairly solu- Ex. No.1681)..... I ble.

Fourth Stage Resin to Et0 Molal Ratio1:15 3 86 4.87 4. 27 3. 86 4. 8713. 02 80 204 V4 Readily sol- Ex. No. 169b uble.

Fifth Stage Resin to EtO V Molal Ratio 1:20. 2 94 3. 75 7.51 2. 94 3. 7513. 20 }4 Soluble. Ex. No. b

Phenol for resin: Para nonylphenol Aldehyd-fdr'resin:Propz'onal'clehy'da- Date [Resin made on pilot plant size batch,approximately 25 pounds, correspondingto 82a of- Patent 459,370 but-thisbatch designated as 171a}- Mix Which is Mix Which Re- Starting Mixfigfigg of Remov'ed fbr mains as Next Sample Starter Max MaY Time Pressme. Temp erahm Solubility Lbs. bs. Lbs. Lbs. Lbs Lbs. Lbs. Lbs. Lbs. lbs,Sol- Res- S01- Res- Sol- Res- -S'ol- Res vent in vent in vent in vent inFirst Stage 10.9 18.0 3.0 2. 65 4.4 0.75 B. 25 13.60 2.25 120 150 M2Insoluble.

Second Stage Resin to EtO. Molal Ratio 1:5--. 8 25 13.60 2.25 8.25 13.6011.50 5. 10 8.35 7.05 3. 5.25 4. 95 174 $6 Becomix g Ex. No. 172bsoluble;-

Third Stage Resin to Et0 Molal Ratio 1:10.- 5 9. 35 5.65 9.35 15.75 3.71 6.14 10.35 1. 94 3. 21 5.40 90 182 M2 Fairiy Ex. No. 1735"-.-soluble.

Faurth Stage Resin to EtO MolalRatio 1:15-. 3.15 5.25 4.45 3.15 5. 2513.45 182 ,-6 Readily Ex. No. 174b soluble.-

Fifth Stage Resin to EtO. Molal Ratio 1:20.. 1.94 3.21 5.40 1.94 3.2110.65 150 $6 .Boluble; Ex. N0. 175b Phenol for resin: Fam-tertiaryiam'ylphenal Aldqhydaforresin: Propzonaldehyde Date [Resin made on pilotplant size batch approximately 25 pounds; corresponding to 34a of Patent2,499,370 but this batch designated 8317671.}

. Mix Which is MixWhich Re- Starting Mix figg figg of Removed for mainsas Nextv Sample Starter Max. Max. Time 1%165511116, llemp elghrsSolubility Lbs Lbs Lbs Lbs Lbs Lbs Lbs Lbs 315mm" Lbs Lbs Lbs Lbs Sol-Res- Sol- Res- Sol- Res- Soi- Resvent in Etc vent in Em vent in m v'entin Etc First Stage Resin to EtO M0131 Ratio 1: 12.6 16.2 12.6 16.2 3. 53. 08 3.96 0.86 9.52 12.24 2.64 150 M2 Insoluble. Ex. N0. 176b SecondStage Resin to EtO. Molal Ratio 1:5." 9.52 12.24 2.64 9.52 12.24 12.895.27 5. 79 7.14 4.25 5.45 5.75 85 171 Becoming Ex. N0. 1775.....soluble.

Third Stage- Resin to EtO. Molal Ratio 1:10.. 6 5 8.3 6.5 8.3 17.75 3.81 4. 87 10.42 2. 59 3. 43 7.33 183 $5 Fairly. solu-v Ex. No. 1785.-. Ible.

Fourth Stage Resin to EtO Molal Rati01:15 4.25 5.45 5.75 4.25 5.45 17.2585 196 )6 Readily. sol- Ex. No. 1795- uble.

Fifth Stage Resin to Et0.. Molal Ratio 1:20 2 69 3.43 7.33 2. 09 3.4314.55 95 P6 Soluble. Ex. No. 1805.-." s

ral.

37 PART 3 It is well'known that certain monocarboxy or tergent-formingacids react with alkali to pro-' duce soap or soap-like materials andare obvious equivalents of the unchanged or unmodified detergent-formingacids. For instance, instead of fatty acids, one might employthechlorinated fatty acids. Instead of the resin acids, one might employthe hydrogenated resin acids. Instead of naphthenic acids, one mightemploy brominated' naphthenic acids, etc. I

The fatty acids are of the type commonly referred to as higher fattyacids; and, of course, this is also true in regard to derivatives of thekind indicated, insofar that such derivatives are obtained from higherfatty acids. The petroleum acids include not only naturally occurringnaphthenic acids, but also acids obtained by the oxidation of wax,paraflin, etc. Such acids may have as many as 32 carbon atoms. Forinstance, see U. S. Patent No. 2,242,837, dated May 20, 1941, toShieldsL1 The monocarboxy detergent-forming esters of the oxyalkylatedderivatives herein described, are preferably derived from unsaturatedfatty acids having 18 carbon atoms. Such unsaturated fatty acids includeoleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. Onemayemploy mixed fatty acids, as for example, the fatty acids obtainedfrom hydrolysis of cottonseed oil, soyabean oil, etc.- Itis our ultimatepreference that the esters of the kind herein contemplated be derivedfrom unsaturated fatty acids, and more especially, unsaturated-fattyacids containing a hydroxyl radical or unsaturated fatty acids whichhave been subjected to oxidation. In addition to synthetic-carboxy-acidsobtained by the oxidation of parafiins or the like, there is thesomewhat analogous class obtained by treating carbon dioxide or carbonmonoxide, in the presence of hydrogen or an'olefine, with steam, or bycausing a halogenated hydrocarbon to react with potassium cyanide andsaponifyingthe product obtained. Such products, or mixtures thereof,having at least 8 and not more than 32 carbon atoms and having at leastone carboxyl group or the equivalent thereof, are suitable asdetergentforming monocarboxy acids; and another analogous class equallysuitable, is the mixture'of carboxylic acids obtained by the alkalitreatment of alcohols of high molecular weight formed in the catalytichydrogenation of carbon monoxide.

As is well known, one need not use a high molal carboxy acid, such asfatty acid, for introduction of the acyl group of acyloxy group. Anysuitable functional equivalent such as the acyl halide, the anhydride,ester, amide, etc., may be employed.

It will be noted that, having obtained a compound which is essentially apolyhydric alcohol, 1. e., an oxyalkylated resin of the type specified,one can produce esters of detergent-forming acids and the more commonpolyhydric alcohols. As is well known, one may well employ notonly thefatty acid itself but also any suitable derivative, for instance, theacyl chloride, the anhydrlde, etc. In some instancestrans-esterification or crossesterification can be employed. Forinstance, the

oxyalkylated derivatives can be heated with the ethyl or methyl ester ofthe selected acid in presence of an alkaline catalyst so as to eliminatemethyl or ethyl alcohol. Such procedure is particularly desirable whena. hydroxylatedv acid-is used, such as ricinoleic acid, hydroxystearicacid, etc. Trans-esterification or cross-esterification can be employedin connection with a glyceride, with 'the formation of glycerine which,under conditions of reaction, probably polymerizes to give polyglycerolsand thus gives a significant and many times a major proportion of thedesired ester. It will be noted that part of what is said herein inregard to-esterification, and particularly in regard to the earlierexamples, is comparable to what is said in our two applications, SerialNos. 518,660 and 518,661 filed January 17, 1944, now abandoned.

As to a rather complete review of the preparation of polyhydric alcoholesters 'of fatty acids, see Chemical Review, 33, 257-349 (1943).

' Example 10 Y An oxyalkylated derivative, such as Example- 1b,preceding. was esterified with oleic acid in .an amount sufficienttoconvert approximately one-.

fourth of the polyglycol radicals into the fatty acid ester- Thehydroxyl value of the oxyalkylated derivative can be calculatedwithoutdetermination, based on the hydroxyl value and weight. of thephenol-aldehyde resin originally.

employed, plus the increase in weight after oxyalkylation. If glycide or,methylglycide is employed, allowance must be made for the polyhydriccharacter of theoxyalkylating reactant; In any event, if desired, thehydroxylzvalue of the oxyalkylated product can be determined by theVerley-Biilsing method, or any other acceptable procedure. Theesterification reaction is conducted in any conventional manner, such asthat employed for the preparation of the higher fatty acid esters ofphenoxyethanol.

Fatty acids, and particularly unsaturated fatty acids, show at leastsome solubility in the oxyalkylated derivatives of the kind shown in theprevious examples, even though this is not necessarily true of theglycerides of the fatty acids. In this instance reference is made to theoxyalkylated derivatives in absence of a solvent. Since esterificationis best conducted in a solution, it is our preference to add xylene,'oreven a higher boiling solvent such as mesitylene, cymene, tetralin orthe like, and conduct esterification insuch consolute mixture. It is notnecessary to add all the fatty acid at one time. One may add a quarteror half the total amount to be esterified, and after such portion of thereactant has combined then add more of the fatty acid. The solubility ofthe fatty acid, of course, increases as the hydroxyl radical is replacedby an ester radical. This is also true'if one resorts totrans-esterification or cross-esterification with the glyceride or lowmolal alcohol ester.

Our preference'is to have present a substantial amount of xylene orhigher boiling waterinsoluble' solvent, and to distill under a refluxcondenser arrangement so that water resulting from esterification isvolatilized and condensed along with the xylene vapor in a suitablyarranged trap. The amount of xylene employed is approximately equal toone-half the weight of the mixed reactants. The water should be removedfrom the trap, either manually or automatically, and the xylene returnedcontinuously for further distillation" Such-reactionis hastenedfif asmall: amount ofzdry 'hydrochloricacid.

gas is continuouslyiinjected-into the esterificar tiont mixture. -When.the reactionis completed,

the. xylene is. removed by: distillation. Small amounts of unreactedfattyacidwcan' be converted into the methyl or: ethyl ester-and removedby vacuum distillation, or permitteclto remain. For,

example, anexcess: of anhydrous ethyl alcohol maybe added andyreactedsoas;to;esterify any. residual. fatty acid, and'then S'LlGhrGXCBSSOf ethylalcohol-may be-distilled ofifas::95 of alcohol-% of water mixture,. andthus; the water resulting fromesterificationi with thealcohol can .beremoved. Although any residual fatty acid;can be eliminated inthe.mannerxabove described, this isof. limited importance'except if one:were pre: paring a drying,oil.fatty. acid derivative which wouldultimately find use-izr varnishproduction. In such. instanceselimination of. allfatty acid isimportant to give enhancedalkali.resistance.

However, even where the amount of: fatty acid employed isstoichiometrically equal to the hydroxyl radicals present, we have notfound it desirable to take any unduev precaution to eliminate any;residualfatty acid. Asamatter of fact, numerous examples include :thepresent one and those subsequently described which yield partial orfractional esters. in which. there is.

present residual hydroxylradicals. Under such circumstances. there; aresubstantially no free fatty acid radicalspresentandthe products obtainedby partial ester-ification instead of complete esterification representthe most valuable type. A sulfonic acid, ,suchas toluene sulfonic acid,may be added in:amounts of. to 1% to act .as a catalyst.

As aspecific example,,900 grams of the xylenecontaining oxyalkylatedresin 12111) were reacted with 70.6 grams of oleic acidin. the presenceof 300 grams of additional xylene :and 20 grams-of; toluene sulfonicacid. Refluxing was continued for three hours or until 4.5 grams ofwaterwere.

evolved.

Example 20 The same procedurewas followedasin Example lc, preceding,exceptthat the amountof oleic acid employed wassuflicient to convertone-- half of the polyglycol radicals intoester form. As a specificexample, 854 grams of xylenecontaining oxyalkylatedresin 1161) werereacted with 141.2 grams of oleic acid in the presence of 200.grams ofadditionalxylene and..15 grams of para-toluene sulfonicacid at 140 C.,until 9.grams of water were evolved, usually about 4 hours.

Example .30

The same procedure wasfoll'owed" as in Example'lc, preceding; exceptthat the amount of oleic acid employed was sufilcient'to. convertthree-fourths of the'polyglycol radicals'into ester form. As aspecifiaexample', 511 grams of" the xylenercontaining oxyalkylated"resin 1251) were reacted with211.8"grams'of ol'eioacid in'the presenceof 200 grams of additional xylene and'l'5 grams of para-toluenesulfonic-acidat 140-145" (3., until M'grams of waterwcreevolved; usuallyabout 3'hours:

' Example 40 The same procedurewasfollowed asin Example 1c, preceding,except that the amount of oleic acid employed was sufficient to convertsubstantially all ofv thepolyglycolradicals into; ester form. As. aspecific; example, .300. grams ohoxy- 40. alkylated resin 1281);containing 37.8 grams of xylene,.wer e refluxed with 70.6 grams of,oleic acidinlthe. presence of 200' grams of additional xyleneand'20'jgra'ms'of f'paraetoluene sulfonic'acid for 6 /4 hours, until"7.9grams. of water were evolved. The resultant was a clear, brown, sticky,

syrup. I

.. Example 5 c.

As a speciflcyexample' 400' grams of xylene-- containingoxyalkylatedresin lllb'were reacted with 93 gramsof. oleic-acid: inpresence of 20 grams" of' para-toluene sulfonicacid and 200 grams ofadded xylene; for- 6% hoursuntil 10.7 grams 'ofwaterthadbeen evolved.The procedure employedwas substantiallythe same as-in Ex ample 1c,preceding:

Example. 6e,

300grams of the xylene-containing oxyalkyl ated resin l22b were reactedwith71.5-gramsof oleic acid in presence'of 20 grams of para-toluenesulfonic acid and 200 gramsof-added xylene, for 2 hours until 6.1 gramsof water had been eliminated. The procedure employed was substantiallythe same as in Example 10, preceding.

Example 70.

300 grams. of thexyleneecontaining oxyalkylr' ated resin identified as.1281) were;reacted.with' 70.8 grams of soyabean fatty acid in presenceof20 grams ofadded paraetolueneisulfonicacidcand 200. grams of added:xylene.

substantially the. same as-zthat; in: Example 10, preceding.

Example 300 grams of the-xylene-containing oxyethylated resin identifiedas 10Gb: were reacted with 109.8 grams of stearic acid in presence of20. grams; of added para-toluene sulfonic acid, and 200. grams ofadditional xylene. The mixture was refluxed for 4 hours until 10 gramsof water were eliminated. The procedure employed was thesame as thatused. in-Example L0,, pre:- ceding.

Efvample 9c gramsof abietic. acid in the. presence of 20 gramsofpara-rtoluene sulfonic-acidand 200 grams of added xylene:f0r. 5 hoursuntil 9.4.grams of water were: eliminated. Theprocedureemployed wasthesame asthatused inExa-mple 1c, preceding.

7 Example-11c 300 grams of the 1 .xyleneecontaining, oxycthylated resindesignated as l06b;were mixed with 103.7 gramsofv naphthenic acid;- inthev presenceof 20: gramspoir. para-toluene sul-fonicacid.- and 200grams ofra'dded; xylene. The particular naphthenic, acid employcdwasone: obtained; from.

The. mixture; was refluxed-for 6. hours-.until Sail-grams of waterwere.eliminated. The procedure employedwas,

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF A DETERGENT-FORMINGMONOCARBOXY ACID OF THE TYPE R''COOH IN WHICH RH IS A MEMBER SELECTEDFROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBON, CHLORINATEDALIPHATIC HYDROCARBON, HYDROXYLATED ALIPHATIC HYDROCARBON,CYCLOALIPHATIC HYDROCARBON, AND BROMINATED CYCLOALIPHATIC HYDROCARBONRADICALS HAVING AT LEAST 7 AND NOT OVER 31 CARBON ATOMS, AND THEALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETICPRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATIONPRODUCTS OF (A) AN ALPHA-BETAALKYLENE OXIDE HAVING NOT MORE THAN 4CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE,PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) ANOXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLEWATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFINCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARDSAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFPHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THEFORMULA